KR20190084947A - Cationic curable adhesive composition for camera module, cured product and conjugate - Google Patents

Abstract

An object of the present invention is to provide a cationically curable adhesive composition which combines low temperature curability and adhesion to engineering plastics (particularly LCP).
(A) Component: A cationic polymerizable resin comprising at least one member selected from the group consisting of an alicyclic epoxy resin and a hydrogenated epoxy resin, (B) component: a thermal cationic polymerization initiator, and (C) A cationic curing property for a camera module characterized by comprising at least one of a rubber filler and a styrene filler comprising at least one member selected from the group consisting of a diene rubber and a (meth) acrylic rubber (excluding a silicone / acrylic copolymer) Adhesive composition.

Description

Cationic curable adhesive composition for camera module, cured product and conjugate

The present invention relates to a cationically curable adhesive composition for a camera module, a cured product of the composition, and a conjugate comprising the composition.

Conventional cationic curable compositions containing an epoxy resin or the like are used for various purposes such as adhesives, encapsulating agents, potting agents, coating agents, conductive pastes and the like because they are excellent in adhesiveness, sealing property, high strength, heat resistance, electrical characteristics and chemical resistance Has come. In addition, the object is used in a wide variety of fields, particularly in electronic devices such as semiconductor panels, liquid crystal displays, organic electroluminescence, flat panel displays such as touch panels, hard disk devices, mobile terminal devices, and camera modules.

According to Japanese Laid-Open Patent Publication Nos. 2009-186756, 2016-044268, 2016-110067, and 2016-122055 (corresponding to pamphlet of International Publication No. 2016-103687) Examples of the adhesion sites of the camera module include an image sensor such as a CMOS and a CCD, a substrate, a cut filter and a substrate, a substrate and a case, a case and a cut filter, and a case and a lens unit .

WO 2005/059002 discloses cationic curing epoxy adhesive compositions for semiconductor device packages, such as CMOS, containing an epoxy resin component, a cationic initiator, a thermal cationic initiator, and a filler.

Engineering plastic such as LCP (liquid crystal polymer), PPS (polyphenylene sulfide), and polycarbonate is used as a material for the case and the lens unit in the camera module. Engineering plastics are plastics having excellent tensile strength even when they are placed in an environment of 100 占 폚 or more for a long time. The cationically curable epoxy adhesive composition disclosed in International Publication WO 2005/059002 has not been satisfactory as an adhesive for a camera module in that adhesion to engineering plastics is poor. Further, the cationic polymerizable adhesive composition for a camera module is required to have low-temperature curing properties (for example, 100 DEG C or less). This is because, if the curing condition is high, a damage to a plastic lens or the like used in the camera module is a concern. The cationically curable epoxy adhesive composition of International Publication WO 2005/059002 discloses that the epoxy adhesive composition is cured by heating at 120 캜 after irradiation with ultraviolet rays according to the embodiment and is not satisfied from the viewpoint of low temperature curability.

It is therefore an object of the present invention to provide a cationically curable adhesive composition which combines low temperature curability and adhesion to engineering plastics (especially LCP).

The present invention overcomes the above-described conventional problems. That is, the present invention is as follows.

[1] Component (A): a cationic polymerizable resin comprising at least one member selected from the group consisting of alicyclic epoxy resin and hydrogenated epoxy resin, (B) component: thermal cationic polymerization initiator, and (C) Based filler for a camera module, which comprises at least one of a rubber filler and a styrenic filler comprising at least one member selected from the group consisting of (meth) acrylic rubber, (meth) acrylic rubber Composition.

[2] The camera module according to [1], which comprises 0.1 to 30 parts by mass of the component (B) and 0.5 to 20 parts by mass of the component (C), based on 100 parts by mass of the component (A) Cationic curable adhesive composition.

[3] The positive curable composition for a camera module according to [1] or [2], wherein the component (B) is a thermal cationic polymerization initiator comprising a salt comprising tetrakis (pentafluorophenyl) Adhesive composition.

[4] The cationically curable adhesive composition for a camera module according to any one of [1] to [3], which further comprises a photocationic polymerization initiator as the component (D)

[5] The cationically curable adhesive composition for a camera module according to [4], wherein the component (D) comprises at least one of an aromatic iodonium-based photopolymerization initiator or an aromatic sulfonium-based photopolymerization initiator.

[6] A cured product of the cationically curable adhesive composition for a camera module according to any one of [1] to [5].

[7] A bonded body obtained by adhering two or more adherends using the cationically curable adhesive composition for a camera module according to any one of [1] to [5].

The cationically curable adhesive composition for a camera module according to one embodiment of the present invention (hereinafter, simply referred to as a composition) is a composition comprising at least one component selected from the group consisting of: (A) an alicyclic epoxy resin and a hydrogenated epoxy resin (C) component: at least one member selected from the group consisting of a diene rubber and a (meth) acrylic rubber (excluding a silicone / acrylic copolymer), a cationic polymerizable resin, a component (B) A rubber filler or a styrene filler. The cationically curable adhesive composition for a camera module having the above-described structure can combine adhesiveness to low-temperature curing properties (for example, 100 ° C or less) and engineering plastics (particularly, LCP).

In the present specification, " X to Y " is used to mean that the numerical values (X and Y) described before and after that are included as a lower limit value and an upper limit value. Unless otherwise stated, the operations and physical properties are measured at room temperature (20 to 25 ° C) / relative humidity of 40 to 50%.

Hereinafter, the present invention will be described in detail.

≪ Component (A) >

The component (A) of the present invention is a cationic polymerizable resin containing at least one member selected from the group consisting of an alicyclic epoxy resin and a hydrogenated epoxy resin. When the component (A) is not included, the low-temperature curability is poor (see Comparative Example 1 to be described later). Here, the cationic polymerizable resin is a compound which causes a crosslinking reaction by cationic species generated in the cationic polymerization initiator. For example, when an epoxy resin and a thermal cationic polymerization initiator are used, the cationic species generated in the thermal cationic polymerization initiator by heating is added to the epoxy group, thereby causing ring-opening polymerization of the epoxy group and crosslinking the epoxy resin. Hydrogenated epoxy resin means a compound obtained by nuclear hydrogenation of an aromatic ring of an aromatic epoxy resin. These may be used singly or in combination of two or more. Among them, from the viewpoint of further enhancing the adhesion to engineering plastics (particularly LCP), the component (A) preferably contains a hydrogenated epoxy resin.

Examples of the alicyclic epoxy resin include, but are not limited to, 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl (3', 4 ' Epoxy-cyclohexanecarboxylate, epsilon -caprolactone-modified 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, 2-epoxy-4-vinylcyclohexane, 1,4-cyclohexanedimethanol diglycidyl ether, epoxyethyl divinylcyclohexane, diepoxyvinylcyclohexane, 1,2,4-triepoxyethylcyclohexane, limonene A silicone, and an alicyclic epoxy group-containing silicone oligomer. These may be used singly or in combination of two or more. Among them, 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate is particularly preferable from the viewpoint of further improving the effect of the present invention.

Examples of commercially available products of the alicyclic epoxy resin include, but are not limited to, Celloxide 2081, Celloxide 2021P, Celloxide 2000, Celloxide 3000, EHPE 3150 (manufactured by Daicel Inc.), TTA21 (manufactured by Jiangsu TetraChem) , X-22-169AS, X-22-169B (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like, but the present invention is not limited thereto.

Hydrogenated epoxy resins include, but are not limited to, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, hydrogenated bisphenol E type epoxy resins, hydrogenated bisphenol A type alkylene oxide adduct diglycidyl Ether, diglycidyl ether of an alkylene oxide adduct of hydrogenated bisphenol F, hydrogenated phenol novolac epoxy resin, hydrogenated cresol novolak epoxy resin, and the like. In particular, hydrogenated bisphenol A type An epoxy resin, a hydrogenated bisphenol F type epoxy resin, and a hydrogenated bisphenol E type epoxy resin are preferable, and a hydrogenated bisphenol A type epoxy resin is particularly preferable. These may be used singly or in combination of two or more.

Examples of commercially available products of hydrogenated bisphenol A type epoxy resins include YX-8000, YX-8034 (manufactured by Mitsubishi Chemical Corporation), EXA-7015 (manufactured by DIC Corporation), ST-3000 (manufactured by Shinil Kagaku Kagaku Kogyo Co., HBE-100 (Shin-Nippon Rika KK), EX-252 (Nagase ChemteX Corporation), and the like. As a commercially available product of the hydrogenated bisphenol F type epoxy resin, there can be mentioned, for example, YL-6753 (manufactured by Mitsubishi Chemical Corporation).

From the viewpoint of further improving the effect of the present invention, it is preferable to use the alicyclic epoxy resin and the hydrogenated epoxy resin together as the component (A), and the mass ratio thereof (alicyclic epoxy resin: hydrogenated epoxy resin) : 30, more preferably 15:85 to 50:50, and even more preferably 25:75 to 40:60.

From the viewpoint of further improving the effect of the present invention, the epoxy equivalent of the component (A) is preferably 50 to 500 g / eq, more preferably 100 to 250 g / eq.

≪ Component (B) >

Component (B) of the present invention is a thermal cationic polymerization initiator and is a compound which generates cationic species by heating. Even when an engineering plastic having low light transmittance is selected as an adherend by containing the component (B), excellent adhesion can be exhibited by thermal curing.

Examples of the component (B) include, but are not limited to, a thermal cationic polymerization initiator (B1) comprising a hexafluoroantimonate anion and a salt comprising a cation, a salt comprising a hexafluorophosphate anion and a cation (B3) comprising a thermal cationic polymerization initiator (B2), a tetrakis (pentafluorophenyl) borate anion and a salt composed of a cation, and the like. Among them, A thermal cationic polymerization initiator (B3) comprising a salt comprising a tetrakis (pentafluorophenyl) borate anion and a cation is preferable. Examples of the cation include a quaternary ammonium cation, and a sulfonium ion in which at least one of the three groups bonded to the sulfur atom is an alkyl group having 1 to 8 carbon atoms. These may be used alone, or two or more of them may be used in combination.

From the viewpoint of satisfactorily satisfying both the low temperature curing property and the adhesion to the engineering plastic, the thermal cationic polymerization initiator (B3) comprising a salt comprising a tetrakis (pentafluorophenyl) borate anion and a cation, (Pentafluorophenyl) borate anion and a salt composed of a quaternary ammonium cation, and the like.

Examples of commercially available products of the thermal cationic polymerization initiator (B1) comprising the hexafluoroantimonate anion and the salt comprising a cation include SI-60L, SI-80L and SI-100L (manufactured by San-in Chemical Industry Co., Ltd.) . SI-110L, SI-180L, SI-B2A and SI-B3A (manufactured by San-Shin Kagaku Kogyo Co., Ltd.) may be mentioned as the thermal cationic polymerization initiator (B2) comprising a salt comprising the hexafluorophosphate anion and the cation. Examples of a commercially available product of the thermal cationic polymerization initiator (B3) containing the tetrakis (pentafluorophenyl) borate anion and the salt comprising a cation include CXC-1821 (manufactured by King Industries) and the like .

The amount of the component (B) in the cationically curable adhesive composition of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 15 parts by mass, per 100 parts by mass of the component (A) More preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass. When it is at least 0.1 part by mass, the low-temperature curing property becomes good, and when it is at most 30 parts by mass, the storage stability becomes good.

≪ Component (C) >

The component (C) of the present invention is at least one of a rubber filler and a styrene filler comprising at least one member selected from the group consisting of a diene rubber and a (meth) acrylic rubber (excluding a silicone / acrylic copolymer). The component (C) has a remarkable effect that it is excellent in adhesion to engineering plastics (especially LCP) without interfering with the curing of the composition (that is, keeping the low temperature curability) by combining with other components of the present invention .

Here, the rubber filler is a rubber-like elastic material at 25 DEG C, and examples thereof include those having a glass transition point (Tg) of less than 25 DEG C. [ Since the engineering plastic has a relatively high crystallinity, it is considered that when the adhesive composition disclosed in International Publication No. 2005/059002 is applied, stress can be applied to the bonding surface and sufficient adhesion can not be exhibited. On the other hand, it is considered that the composition according to the present invention is able to exhibit excellent adhesion by relaxing the stress by containing a rubber filler.

Examples of the diene rubber include a polyisoprene rubber, a polybutadiene rubber, a styrene butadiene rubber, an acrylonitrile butadiene rubber, a polychloroprene rubber, and hydrogenated products thereof. From the viewpoint of further improving adhesion to engineering plastics Of these, polybutadiene rubber, styrene butadiene rubber and acrylonitrile butadiene rubber are preferable, and polybutadiene rubber or acrylonitrile butadiene rubber is more preferable, and polybutadiene rubber is particularly preferable. These may be used alone, or two or more of them may be used in combination.

(Meth) acrylic rubber refers to a polymer obtained by polymerizing (meth) acrylic acid ester alone or in combination with a monomer copolymerizable therewith (except for a silicone acrylic copolymer), and examples thereof include acrylic acid ester · 2-chloroethyl vinyl ether (ACM), acrylic rubbers such as acrylate ester / acrylonitrile copolymer (ANM), and the like. Here, in the definition of the (meth) acrylic rubber, the silicone / acrylic copolymer is excluded because sufficient adhesion to the engineering plastic can not be obtained (see Comparative Example 5 to be described later).

Examples of the (meth) acrylic esters include ethyl (meth) acrylate, butyl (meth) acrylate, and methoxyethyl (meth) acrylate. Examples of the monomer copolymerizable with the (meth) acrylic acid ester include 2-chloroethyl vinyl ether, acrylonitrile, and the like.

The component (C) preferably contains at least one of a polybutadiene rubber and an acrylic rubber, and more preferably a polybutadiene rubber, from the viewpoint of further improving the adhesion to engineering plastics.

The styrene type filler is a polymer obtained by polymerizing or copolymerizing at least one kind of styrene derivative (e.g., styrene,? -Methylstyrene, divinylbenzene) with a monomer copolymerizable therewith, and has a glass transition point (Tg) Is a polystyrene-based filler of, for example, 200 DEG C or less. Specific examples of the styrene-based filler include styrene-glycidyl methacrylate copolymer, styrene-divinylbenzene copolymer and the like, preferably styrene-divinylbenzene copolymer. Commercially available products include Mafrup G-1005S (manufactured by Nichiyu Co., Ltd.) and Pine Pearl PB-3006E (manufactured by Matsuura Co., Ltd.). These may be used alone or in admixture of two or more.

On the other hand, by dispersing the component (C) of the present invention in the component (A) of the present invention in advance, it is also possible to facilitate dispersion in the composition.

The average particle diameter of the component (C) is preferably 0.01 to 5 占 퐉, more preferably 0.05 to 1 占 퐉, and particularly preferably 0.1 to 0.6 占 퐉. When the thickness is not less than 0.01 탆, the viscosity of the adhesive composition is not increased and the workability is good. When the thickness is not more than 5 탆, the adhesive composition is preferable. The average particle diameter is measured by a laser refraction / scattering method (50% volume average particle diameter).

The amount of the component (C) to be added is preferably 0.1 to 50 parts by mass, more preferably 0.3 to 30 parts by mass based on 100 parts by mass of the component (A), and the adhesion to engineering plastics More preferably from 0.5 to 20 parts by mass, and even more preferably from 2 to 12 parts by mass, from the viewpoint of further improvement. Among them, the lower limit is preferably 4 parts by mass or more, 5 parts by mass or more, or 6 parts by mass or more, and the upper limit is preferably 10 parts by mass or less, 9 parts by mass or less, or 8 parts by mass or less.

≪ Component (D) >

The present invention may further contain a photocationic polymerization initiator as the component (D) within the range not impairing the characteristics of the present invention. (D), it is possible to harden the core portion of the heat after hardening by light. Thus, a cured product crosslinked to the core portion is obtained, and more stable adhesion can be exhibited. Gwangyang Ion Polymerization Initiator is a compound that generates cationic species by irradiation with active energy rays. The component (D) is not particularly limited. For example, when a salt containing tetrakis (pentafluorophenyl) borate anion is selected as the component (B), it is preferable that the photocuring property, the thermosetting property, It is preferable to include at least one of an aromatic iodonium-based photopolymerization initiator or an aromatic sulfonium-based photopolymerization initiator. These may be used alone, or two or more of them may be used in combination. Among them, it is preferable to include an aromatic iodonium-based photopolymerization initiator.

Examples of the aromatic sulfonium-based photopolymerization initiator include a photocationic polymerization initiator including sulfonium ions in which all three groups bonded to sulfur atoms are aryl groups (e.g., phenyl groups). The aromatic iodonium-based photopolymerization initiator includes a photopolymerization initiator containing an iodonium ion in which two groups bonded to an iodine atom are aryl groups (for example, phenyl group). On the other hand, the initiator which generates a cationic species by any one of heat and active energy rays is classified as a component (B) in the present invention.

Examples of the aromatic sulfonium-based photopolymerization initiator include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4 Bis [diphenylsulfonium] diphenyl sulfide-bishexafluorophosphate, 4,4'-bis [di (? - hydroxyethoxy) phenylsulfonio] diphenylsulfide- bishexafluoro (Dihydroxyethoxy) phenylsulfonium] diphenylsulfide-bishexafluorophosphate, 7 [di (p-toluyl) sulfo ] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthonetetrakis (pentafluorophenyl) . But are not limited thereto. These aromatic sulfonium-based photopolymerization initiators may be used singly or in combination.

SP-170, SP-172 (manufactured by ADEKA), CPI-100P, CPI-101A, CPI-110B, CPI-200K and CPI-210S UVI-6974 (manufactured by Union Carbide), DTS-200 (manufactured by Midori Kagaku Co., Ltd.), and the like can be given.

Examples of the aromatic iodonium-based photopolymerization initiator include diphenyl iodonium tetrakis (pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate diphenyliodonium hexafluoroantimonate, di (4- Nonylphenyl) iodonium hexafluorophosphate 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate. Among them, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate is preferable. These may be used alone or in combination.

Examples of commercially available aromatic iodonium-based photopolymerization initiators include IGACURE 250 (manufactured by BASF), PI-2074 (manufactured by Rhodia), B2380, B2381, D2238, D2248, D2253 and I0591 (manufactured by Tokyo Kasei Kogyo Kogyo) 113, WPI-116, WPI-169, WPI-170 and WPI-124 (manufactured by Wako Pure Chemical Industries, Ltd.).

The amount of the component (D) to be incorporated in the cationically curable adhesive composition of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the component (A) Mass part, and still more preferably 1 to 5 mass parts. When the amount is more than 0.1 part by mass, the photocurability becomes good. When the amount is less than 30 parts by mass, the component (A) tends to be dissolved.

<Optional ingredients>

Further, the cationically curable adhesive composition of the present invention may contain various additives such as an aromatic epoxy resin, an oxetane compound, a vinyl ether compound, a colorant such as a pigment and a dye, a sensitizer, a silane coupling agent, a polyol compound, Inorganic compounds having an average particle diameter of 0.001 to 100 μm such as peroxide, thiol compound, preservative stabilizer, calcium carbonate, magnesium carbonate, titanium oxide, magnesium hydroxide, talc, silica, alumina, glass, aluminum hydroxide, boron nitride, aluminum nitride, A light stabilizer, an ultraviolet absorbent, a defoaming agent, a foaming agent, a releasing agent, a leveling agent, a rheology modifier, a tackifier, a filler, a conductive agent such as filler and silver, a flame retardant, a plasticizer, an organic solvent, , A hardening retarder, a polyimide resin, a polyamide resin, a phenoxy resin, a cyanate ester, a polyvinyl Additives such as a butyral resin may be blending an appropriate amount. By these additions, a cationically curable adhesive composition having excellent resin strength, adhesive strength, flame retardancy, thermal conductivity, workability and the like and a cured product thereof can be obtained. Among them, it is preferable to further include a silane coupling agent from the viewpoint of further improving the adhesion to engineering plastics.

In the present invention, in addition to the alicyclic epoxy resin and the hydrogenated epoxy resin of component (A), an aromatic epoxy resin, oxetane compound, vinyl ether compound and the like can be used in combination.

Examples of the aromatic epoxy resin include aromatic bisphenol A type epoxy resins, aromatic bisphenol F type epoxy resins, aromatic bisphenol E type epoxy resins, diglycidyl ether of aromatic bisphenol A type alkylene oxide adducts, aromatic bisphenol F type alkyl A diglycidyl ether of an aromatic adduct of an alkylene oxide adduct, an aromatic novolak-type epoxy resin, a urethane-modified aromatic epoxy resin, a nitrogen-containing aromatic epoxy resin, a polybutadiene or And rubber-modified aromatic epoxy resins containing nitrile-butadiene rubber (NBR) and the like. These may be used singly or in combination of two or more.

Examples of commercial products of aromatic epoxy resins include jER 825, 827, 828, 828EL, 828US, 828XA, 834, 806, 806H, 807, 604, and 630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 830, EXA-830LVP, EXA- N-655-EXP-S, N-665-EXP-S, N-685-EXP-S, N-680, N-695, (Manufactured by ADEKA Corporation), Denacol EX614B, EX411 (manufactured by DIC Corporation), N-775, N-865 (manufactured by DIC Corporation), EP4100, EP4000, EP4080, EP4085, EP4088, EP4100H, EP4901HF, EP4000S, EP4000L, EP4003S, EP4010S, , EX314, EX201, EX212, and EX252 (manufactured by Nagase ChemteX Corporation), but the present invention is not limited thereto. These may be used alone or in combination of two or more.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) , [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethoxy) Ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol Ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl Ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl -Oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol Trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis -3-oxetanylmethyl) ether, and the like. Examples of commercially available oxetane compounds include OXT-212, OXT-221, OXT-213 and OXT-101 (manufactured by Toa Gosei Co., Ltd.). These may be used singly or in combination of two or more.

Examples of the vinyl ether compound include 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, Butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, Vinyloxyethoxy) ethyl methacrylate, and 2- (2-vinyloxyethoxy) ethyl methacrylate. Examples of commercially available products of the vinyl ether compound include NPVE, IPVE, NBVE, IBVE, EHVECHVE (manufactured by Nippon Carbide Industries Co., Ltd.), HEVE, DEGV, HBVE (manufactured by Maruzen Petrochemical Co., Ltd.), VEEA . These may be used singly or in combination of two or more.

Examples of the sensitizer include 9-fluorenone, anthrone, dibenzosuberone, fluorene, 2-bromofluorene, 9-bromofluorene, 9,9-dimethylfluorene, 2-fluorofluorene, 2- Iodine fluorine, 2-fluorene amine, 9-fluorene, 2,7-dibromofluorene, 9-aminofluorene hydrochloride, 2,7- diaminofluorene, 9,9'- 2-methyl-1-phenylpropane-1-carboxaldehyde, 9-fluorene carboxyaldehyde, 9-fluorenylmethanol, 2-acetylfluorene, benzophenone, diethoxyacetophenone, (2-hydroxy-2-propyl) ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl- 2-methyl-1- [4- ((4-fluorophenyl) 1-methylvinyl) phenyl] propanone oligomer, a nitro compound, a pigment, and the like. The addition amount is not particularly limited, but it is necessary to refer to the absorption wavelength and the molar extinction coefficient.

Examples of the silane coupling agent include vinyl group-containing silane coupling agents such as vinyltris (? -Methoxyethoxy) silane, vinyltriethoxysilane and vinyltrimethoxysilane,? -Methacryloxypropyltrimethoxy (Meth) acrylic group-containing silane coupling agents such as silane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl- Amino group-containing silane coupling agents such as methoxy silane, ethoxy silane and other amino group-containing silane coupling agents, and other? -Mercaptopropyl trimethoxy silane and? -Chloropropyl trimethoxy silane. Among them, a glycidyl group-containing silane coupling agent is preferably used, and among the glycidyl group-containing silane coupling agents, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are preferable. These may be used alone, or two or more of them may be used in combination.

The polyol compound may be added to adjust the curing rate or increase the adhesion. Examples of the polyol compounds include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,9-nonanediol, neopentyl glycol, tricyclodecane dimethylol, cyclohexanedimethanol, Aliphatic polyols such as ethylene glycol, propylene glycol, glycerin, hydrogenated polybutadiene polyol, and hydrogenated dimer diol; and aliphatic polyols such as diethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane polyethoxytriol, (Poly) ether polyol, polyester polyol compound, and polycaprolactone polyol compound having one or more ether bond (s) such as epoxy triol, bisphenol A polyethoxydiol, bisphenol F polyethoxydiol, and ditrimethylol propane , Polyol compounds having a phenolic hydroxyl group, and polycarbonate polyols such as polycarbonate diol. All.

<Curing method and cured product>

The present invention also provides a cured product of the above cationically curable adhesive composition for a camera module. In the case of obtaining a cured product by heating and curing the cationically curable adhesive composition of the present invention, the heating temperature is not particularly limited, but is preferably 45 ° C or more and less than 100 ° C, more preferably 50 ° C or more Lt; 0 &gt; C. The heating time is not particularly limited, but is, for example, preferably 5 to 120 minutes, and more preferably 10 to 60 minutes. In addition, the composition according to the present invention can be cured by irradiation with active energy rays by including the component (D). Examples of the active energy ray in this case include ultraviolet rays, electron rays, visible rays, and the like, but are not particularly limited. The accumulated light quantity of the active energy ray is preferably from 300 to 100000 mJ / cm 2, and the wavelength of the active energy ray is preferably from 150 to 830 nm, more preferably from 200 to 400 nm. On the other hand, as the curing method of the cationic curable adhesive composition of the present invention, active energy ray irradiation and heating may be used in combination.

<Applications>

The use of the cationically curable adhesive composition of the present invention is a camera module. Examples of the adhesive portion of the camera module include a gap between an image sensor such as a CMOS and a CCD and a substrate, a cut filter and a substrate, a substrate and a case, a case and a cut filter, and a case and a lens unit . The material of the case and the lens unit is not particularly limited, but engineering plastics such as LCP (liquid crystal polymer), PPS (polyphenylene sulfide), polycarbonate and the like can be mentioned from the viewpoint of excellent moldability . The cured product of the cationically curable adhesive composition of the present invention has excellent adhesion to these engineering plastics (especially LCP). That is, another embodiment of the present invention is a camera module comprising a cured product of the cationically curable adhesive composition.

<Junction>

The present invention also provides a bonded body formed by adhering two or more adherends using the above cationically curable adhesive composition for a camera module. The adherend is not particularly limited, but engineering plastics such as LCP, PPS, polycarbonate and the like can be mentioned, among which LCP is preferable. Therefore, one preferred embodiment of the present invention is a bonded body obtained by bonding two or more LCPs using the above cationically curable adhesive composition for a camera module.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited by the following examples.

&Lt; Preparation of cationic curable adhesive composition >

Each component was taken in a mass part shown in Table 1, mixed with a planetary mixer at room temperature under a shade for 60 minutes to prepare a cationically curable adhesive composition, and various physical properties were measured as follows.

&Lt; Component (A) >

a1: hydrogenated bisphenol A type epoxy resin (YX8000, epoxy equivalent: 205 g / eq, manufactured by Mitsubishi Chemical Corporation)

a2: 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celloxide 2021P, epoxy equivalent: 137 g / eq, manufactured by Daicel Inc.)

&Lt; Comparative composition of component (A) >

a '1: aromatic bisphenol A type epoxy resin (jER807, manufactured by Mitsubishi Chemical Corporation)

&Lt; Component (B) >

b1: Thermal cationic polymerization initiator (CXC-1821, manufactured by King Industries) containing a tetracis (pentafluorophenyl) borate anion and a salt comprising a quaternary ammonium cation,

&Lt; Component (C) >

c1: Polybutadiene rubber filler having an average particle diameter of 0.2 탆 (Tg less than 25 캜)

c2: a styrene-butadiene rubber filler having an average particle diameter of 0.1 mu m (Tg less than 25 DEG C)

c3: average particle diameter 0.3 탆 Acrylic rubber filler (Tg less than 25 캜)

c4: Acrylonitrile-butadiene rubber filler (Tg less than 25 占 폚) having an average particle diameter of 0.3 占 퐉

c5: a styrene type filler (Tg 100 DEG C) of a styrene-divinylbenzene copolymer having an average particle diameter of 0.6 mu m,

&Lt; Comparative component of component (C) >

c'1: hydroxyl-terminated polyisoprene (Poly ip (registered trademark), manufactured by Idemitsu Kosan Co., Ltd.) which is liquid at 25 占 폚,

c'2: a hydroxyl group-containing polybutadiene (Poly bd (registered trademark), manufactured by Idemitsu Kosan Co., Ltd.)

c'3: Silicone-acrylic copolymer rubber filler having an average particle diameter of 0.4 mu m

c'4: Urethane rubber filler having an average particle diameter of 0.3 mu m

c'5: a flake acrylic resin having no rubber elasticity at 25 DEG C (ARUFON (registered trademark) UG-4035, manufactured by Toa Gosei Co., Ltd.)

&Lt; Component (D) >

d1: photoionization polymerization initiator containing aromatic iodonium salt (PI-2074, manufactured by Rhodia)

&Lt; Other components >

Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.).

Test methods used in Examples and Comparative Examples are as follows.

&Lt; Low temperature curing test &

0.1 g of each cationically curable adhesive composition was dropped onto a hot plate set at 80 占 폚, and after 30 minutes, the cured product was contacted with a sharp-pointed glass rod, and the curability of the composition was visually evaluated based on the following criteria. If it is? In the following criterion, the low-temperature curing property can be good. The results are shown in Table 1.

[Evaluation standard]

○: There is no attachment on the rod.

X: There is an attachment on the rod.

&Lt; Adhesion to Engineering Plastics >

A test piece made of LCP (manufactured by Polyplastics Co., Ltd., VECTRA E130i, manufactured by Polyplastics Co., Ltd.) having a width of 250 mm, a length of 10 mm and a thickness of 3 mm was attached to the back surface of a stainless steel washer having a hole of 0.5 mm in thickness and a diameter of 6.1 mm and made of polytetrafluoroethylene tape. ). Next, each cation-curable adhesive composition was applied to the interior of the washer, and cured by heating at 80 DEG C for 1 hour. Thus, a test piece to which a cured product of an LCP test piece and a cation-curable adhesive composition were adhered was obtained. The chip strength [N / mm &lt; 2 &gt;] was measured with a push-pull gauge using the test piece. The results are shown in Table 1.

The preferable chip strength in the present invention is 6.0 N / m 2 or more, more preferably 7.0 N / mm 2 or more, still more preferably 8.0 N / mm 2 or more, particularly preferably 10 N / mm 2 or more For example 20 N / mm &lt; 2 &gt;). On the other hand, &quot; unmeasurable &quot; in Table 1 means that the cation-curable adhesive composition was not cured even after heating at 80 DEG C for 1 hour, and it was impossible to carry out this test.

[Table 1]

It can be seen from Examples 1 to 11 that the cationically curable adhesive composition of the present invention combines low temperature curability (100 DEG C or less) and adhesion to engineering plastics (LCP).

Comparative Example 1 is a composition containing only an aromatic bisphenol A type epoxy resin without any of the alicyclic epoxy resin or hydrogenated epoxy resin which is an essential component of the component (A) of the present invention, but the composition having a remarkably low low- Able to know. In addition, it can be seen that Comparative Example 2 is poor in adhesion to a composition that does not include the component (C) of the present invention, and to engineering plastics (LCP). In Comparative Examples 3 to 5, a composition using a copolymer of hydroxyl-terminated polyisoprene or a hydroxyl-group-containing polybutadiene liquid at 25 ° C or silicone-acrylic copolymer having an average particle diameter of 0.4 μm at 25 ° C in place of the component (C) , The adhesion to engineering plastics is poor. Further, Comparative Example 6 was a composition using urethane rubber instead of the component (C) of the present invention, but the low temperature curability was remarkably low. In Comparative Example 7, a composition using a flaky acrylic resin instead of a rubber elastic body at 25 캜 was used instead of the component (C) of the present invention, but the low temperature curability was remarkably low.

Industrial availability

INDUSTRIAL APPLICABILITY The present invention is industrially useful in that it is a cationically curable adhesive composition having low temperature curability and adhesion to engineering plastics (especially LCP), and is applicable to adhesives for camera modules.

On the other hand, the application of the present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the spirit of the present invention.

The present application is based on Japanese Patent Application No. 2016-225225 filed on November 18, 2016, the disclosure of which is incorporated by reference in its entirety.

Claims (7)

(A): a cationic polymerizable resin containing at least one member selected from the group consisting of an alicyclic epoxy resin and a hydrogenated epoxy resin,
(B): a thermal cationic polymerization initiator, and
(C): at least one of a rubber filler or a styrene filler comprising at least one member selected from the group consisting of a diene rubber and a (meth) acrylic rubber (excluding a silicone / acrylic copolymer) Cationically curable adhesive composition for a camera module. The method according to claim 1,
Wherein the composition contains 0.1 to 30 parts by mass of the component (B) and 0.5 to 20 parts by mass of the component (C) based on 100 parts by mass of the component (A). 3. The method according to claim 1 or 2,
Wherein the component (B) is a thermal cationic polymerization initiator comprising a salt comprising a tetrakis (pentafluorophenyl) borate anion and a cation. 4. The method according to any one of claims 1 to 3,
(C), and further contains a cationic polymerization initiator as a component (D). 5. The method of claim 4,
Wherein the component (D) comprises at least one of an aromatic iodonium-based photopolymerization initiator or an aromatic sulfonium-based photopolymerization initiator. A cured product of the cationically curable adhesive composition for a camera module according to any one of claims 1 to 5. A bonded body obtained by adhering two or more adherends using the cationically curable adhesive composition for a camera module according to any one of claims 1 to 5.